(Phosp)hole in one: A palladium‐catalyzed synthesis for directly assembling phosphole skeletons from triarylphosphines through CH and CP bond cleavage was developed. This approach overcomes several of the limitations of the so far reported methods. Phospholes bearing a range of functionalities (including Br, F, CO2Me, Ac, and CN) and an array of fused rings (naphthalenes, anthracenes, furans, and pyrroles) can be easily synthesized.

A rhodium-catalyzed coupling reaction of 2-trimethylsilylphenylboronic acid with internal alkynes is developed for the synthesis of 2,3-disubstituted benzosilole derivatives. A range of functional groups, encompassing ketones, esters, amines, aryl bromides, and heteroarenes, are compatible, which provides rapid access to diverse benzosiloles. Sequential 2-fold coupling enables modular synthesis of asymmetrically substituted 1,5-dihydro-1,5-disila-s-indacene, a π-extended molecule of interest in organic electronics. In terms of the mechanism, the reaction involves cleavage of a C(alkyl)-Si bond in a trialkylsilyl group, which normally requires extremely harsh conditions for activation. Mechanistic studies, including effects of substituents, reveal that C-Si bond cleavage does not proceed through a hypercoordinated silicon species, but rather through a rhodium-mediated activation process. The potential use of the reaction in catalytic asymmetric synthesis of Si-chiral benzosiloles is also demonstrated.

The palladium-catalyzed synthesis of dibenzofused six-membered phosphacycles via carbon-phosphorus bond cleavage is developed. This method is compatible with a range of functional groups, such as esters, amides, and carbamates, which is in sharp contrast to the limitations of the classical method using organolithium reagents.

Pd(ii)-catalyzed synthesis of dibenzothiophene derivatives has been developed. The reaction proceeds through the cleavage of carbon–hydrogen and carbon–sulfur bonds.